Vegetable textile material and process for producing same



Patented Dec, 31, 1929 I PATENT OFFICE LEON LILIENFELD, F VIENNA, AUSTRIA VEGETABLE TEXTILE MATERIAL AND PROCESS FOR PRODUCING Sm No Drawing. Application filed July 23, 1924, Serial No. 727,809, and in Austria April 4, 1924.

This invention relates to, a process, for improving textile materials of vegetable origin.

According to the invention very valuable properties are conferred, upon woven and spun material of vegetable origin by treating them in presence of alkalies with a halohydrin, for example a mono-halo-hy'drin of a poly-alcohol. This process imparts to the materials a silky gloss of great brilliance and a pleasing finish of elasticyfeel.

The invention consistsin treating with a halo-hydrin, for example a mono-halo-hydrin of a poly-alcohol in presence of alkali, spun or woven material consisting of or containing a vegetable fibre, particularly cotton. The material may be treated with the halo-hydrin and with the alkali either simultaneously or in either sequence;

Among the alkalies which can be used, the

most important are the caustic alkalies.

Alkali sulphides may, however, be used,

although the results obtained are usually less satisfactory. The alkali sulphides when dissolved in water are largely hydrolyzed, giving a strong alkaline solution containing alkali hydroxide. Therefore the use of alkali sllphides involves the use of alkali hydrox- There may be treated according to the invention all vegetable fibres, such as linen,

flax, hemp, ramie, jute, and especially cotton, .in the form of pure vegetable (for ex ample, pure cotton) or mixed goods, in the form of yarn in skeins or cops, or in the form of warps. I r

The textile goods consisting of or containing the vegetable fibre may be treated according to the invention either in the crude state or after a preliminary treatment (for instance, boiling, or heating under pressure with sodium carbonate solution or dilute alkali solution or both), either moistened or unmoistened, with or without removing the fatty constituents, either unbleached or after bleaching agent, and with or without mer cerizing. The material may also be. previously prepared in known manner by treatment with a hydrolyzing or gelatinizin agent (for example with astrong minera .its practical applicationv which follow.

bleaching with an oxidizing or reducingacid such as sulphuric acid of 4960 Baum gravity, phosphoric acid of -57 Baum gravity, hydrochloric acid of 24 Baum gravity, or nitric acid of43-45"Baum gravity or more, with an ammoniacal solution of 55 cuprie oxide, or with a cold or hot solution of calcium thiocyanate or other thiocyanate) The preliminary treatment may also consist .in a combination of two or more of these PI'OCBSSGS. I 0

The conditions under which the process is, carried outaccording to the invention may vary within wide limits, and the invention is not limited .to the illustrative examples of As example, the following methods of carrying out the .invention are given.

The first method consists in treating the woven or spun material first witha solution of an alkali and then acting on it with a halo-hydrin, .s'uch as armonochlorhydrin or a-dichlorhydrin or ethylene-chlorhydrin. The textile material may be treated with the alkali solution in various ways; for example by dipping or soaking it in a small or large excess of the solution; by dipping or soaking it in the solution and removing the excess of alkali solution by squeezing, centrifuging or the like; loy impregnating it in an impregnating mill, jigger or the l1ke;'by '80' padding it between smooth or engraved roll ers in a padding-machine; by coating by means of. closely engraved rollers in' a. Rouleaux machine, advantageously with the' addition of a thickening agent; by spraying, or by any other known method.

As alkali solution there may be used, for example, a solution of caustic soda of 10-50 per cent strength; a solution of caustlc soda of 12-40 per cent strength has been found very suitable.

The quantity of alkali solution with which the material .is to be impregnated, or which is to be retained by the material, may be varied within wide limits. Thus, for instance, satisfactory results have been obtained when this quantity is. fro1n2 to 10 times the weight of the textile material. As a rule, a-qu'antit'y of from 2 to 4 times the weight of the material will be found to be suliicient.

The temperature of the alkali solution may also be chosen from a wide range. Useful results are obtained at temperatures of from 10 C, to 50 C. according to the strength of the solution. Generally, if the solution is not too weak, theprocess may be conducted at room temperature.

In order that the alkali solution may penetrate the fibres thoroughly, and increase the lustre, the woven or spun material may be caused to pass between rollers during the treatment with the solution, or it may otherwise be subjected to a high pressure. If desired, the alkali solution may contain some alcohol. The textile material which has been treated with alkali is then treated with a halo-hydrin of a poly-alcohol, either immediately after the alkali treatment, or after standing (ripening) at room temperature for a short or long period, and either in the wet state or afterit has previously been partly or completely dried. The halo-hydrin may be brought, into contact with the material which has been treated with the alkali solution either as such, or dissolved in a suitable solvent, or suspended in an indifferent '-Briti sh gum, albumen or the like. The halo-hydrin may be'added in various ways to the material which has been treated with the solution of alkali. The material may be impregnated or coated with the halohydrin, or a solution or emulsion thereof (in which case any excess may be removed, if desired, by pressing or centrifuging), or the halo-hydrin, or a solution or emulsion there'- of may be rolled into the material. Any

other method 1 may however be employed, such as spraying; In order that the distribu-- tion of the halo-hydrin throughout'the tex tile material may be as uniform as possible, the material may be passed through one or 'more pairs of rollers ,duringthe treatment, or may be subjected to pressure by. other means. i

For introducing the halo-hydrin there'may be used any suitable apparatus known in the art of finlshing or printing textiles. In practice, there are no limits to the quantity of the halo-hydrin which maybe the invention is not limited to this amount. In most cases it IS sufliclent to use a much smaller quantity, for instance 0.3 0.75 m01ecular proportions of a halo-hydrin or even less, for'each molecular proportion of caustic alkali.

The material which has been treated with v the halo-hydrin is then either directly washed soon after addition of the halo hydrin or after it has been in contact with it for a short or long period (for example -24 hours) at room temperature or at a higher temperature (for example -100 U), and, if desired, after previously having been dried, or it may advantageously be before or after Washing.

Any of the subsidiary operations usual in mercerization or proposed for this purpose may also be used in the present invention, for example .lustring, pressure, mechanical beating,and the like.

In order to produce a high grade silky lustre, it is essential that the textile fibre should be stretched. It may be stretched throughout all the operations, that is," from the impregnation with the alkali solution at the commencement, to the washing and drying operation. The material may also be stretched only during the action of the alkali solution or of the halo-hydrin, or it may be stretched after the impregnation with the alkali solution, and may remain stretched during the action of the halo-hydrin, during the treatment with the acid, salt, or the like, and during the washing and optionally final drying. Or it. may be stretched only after the action of the alkali solution and of the halo-hydrin, for the treatment with the acid or salt, for the washing operation, and if necessary for the drying operation. Or the stretching may be applied only during apart of the rocess, for instance, so that the material is stretched during the treatment with the alkali solution, during the treatment with an acid or salt, and during the final washing, but not stretched during the action of the mono-halo-hydrin.

The second method of carrying out the inyention consists in reversing the order of the operations of the first method; that is to say,

the textile material is first treated with the 'halo-hydrin as such, or with a solution or a suspension thereof, and is then introduced into the alkali solution or impregnated, coated, or sprinkled, or sprayed therewith.

Since the halo-hydrins have no action on the fibrein absence of alkali, the treatment with alkali solution may follow the treatment with the halo-hydrinj at leisure. After the material has beenbrought into contact with the alkali solution, the halo-hydrin is allowed to act for a certain time; this action may proceed at room temperature or at a higher temperature. In respect of the other conditions such as the quantitative proportions, the tem-- eratures, the duration of the reaetion,"the

retching, and the finishing of the material, the conditions given in the first method of' carrying out the process are equally applicable, y

By an appropriate selection of the working conditions, there may be obtained by the present invention silk-like effects which are far superior to those which can be obtained by the usual methods of mercerization. In addition to the silky lustre, the woven or spun material possesses a finish which has a valuable, elastic feel. The silky lustre may be improved by one or more repetitions of the process.

The process according to the invention is also suitable for producing patterns, for which the following methods are of consequence:

1. Before the treatment with the alkali solution, a pattern is printed or stencilled on the material by means of a reserve paste which prevents either mechanically or chemically the absorption of the alkali solution. Materials suitable for the reserve are, for instance, albumen, gums, acids (such as acetic .acid, citric acid, tartaric acid, or an inorganic acid), alum, aluminium sulphate, ammonium sulphate, or other salts. The material is then treated with alkali solution and a halo-hydrin according to the method described in illustration of the first method' of carrying out the invention. This modification of the process permits the production of a lustrous pattern upon a dull background'or vice versa.

2. The alkali solution, mixed with a suitable thickening agent (such as starch, denatured albumen, a cellulose-hydrate which is soluble in alkali, an alkyl or oxyalkyl-cellulose derivative which is soluble in alkali solutions or in water, or a cellulose-hydroxyparafiin-monocarboxylic acid or the like), is printed in any desired pattern on the woven material, which is then treated'wi-th a halohydrin as already described. The eifects obtained resemble those obtained according to 1.

3. After treatment with the alkali solution and if necessary after drying, the material is printed with a reserve which prevents, either mechanically or chemically, the reaction between the alkali-cellulose and the halohydrin. There may be used for this purpose, for example, an acid, albumen, kaolin, z ncwhite, or the like. There may also be added to the reserve paste a dyestulf or pigment. After printing withthe. reserve, the materla is treated with a halo-hydrin as in the first 1 the invention, and is method of carrying out then treated with an acid or salt, and dried.

"method of carrying out .halo-hydrin, I 'thereof may be rolled on to or into thevtexpended in a suitable thickening medium (for example British gum, starch or dextrin) with or Without the addition of a dyestufli', and then finishing the material according to the first ly lustrous effects on a less ground may thus be obtained. 4

, 5-. A halo-hydrin in the form of a solution or suspension is printed on the woven material with the aid of a thickening agent, and the material is then subjected, with or without drying, to the action of the alkali solu-- tion. The effects are similar to those obtained in 3 and 4.

lustrous backthe invention. High-.

The following examples illustrates the invention the parts being by weight (a) Bleached or unbleached cotton fab:

r'ic or yarn is treated with caustic soda solution of 25 10 per cent strength for a period of from 5 minutes to 12 hours. at room temperature, and the excess of the solution removed by wringing or centrifuging, until the mate rial retains about 2 A 3 times its weight or any other desired proportion, of the solution. The impregnated material is then treated either immediately or after it has been allowed to stand for 3-72 hours, with a-monochlorhydrin or a-dichlorhydrin chloro-propylene-glycol) or ethylenechlorhydrin, either alone,

strength in a solution of British guin of 20-25 per cent strength. The yarn or fabric may be impregnated or coated on one or both sides with the .halo-hydrin, or the solution or suspension thereof, or the or the solution or suspension There is practically no limit tile material. to the quantity dichlorhydrin or ethylenechlorhydrin ma be incorporated with the yarn or which has been impregnated with caustic soda solution. For reasons of economy, however, it is advisable to "use a quantity equal to not more than A to 1 times the weight of the cotton oods, particularly as excellent effects may e obtained with this amount or even with a smaller amount. After the material has been in contact with a-monochlorwhich 1 =hydrin or a-dichlorhydrin or ethylenechlorhydrin for a short period (e. g. 10 minutes), or for a longer period (for example 12 hours) ,it is washed and dried or introduced or in the form of a solution of 10-50 per cent strength in alcohol, or' in the form of a solution or a suspension of 10-50 per cent of a-monochlorhydrin or afabric ric or yarn should be stretched for at least a into a dilute solution (for example of -20 per cent strength) of sulphuric or acetic acid, or into a solution of ammonium chloride or ammonium sulphate of 30 per cent strength, or into any other precipitating bath known in the viscose industry; it is allowed to remain in the bath for a short period such as-5 minutes), or for a longer period such as several hours), and is then washed and dried. The fixing agent may be applied to the fabric by sprinkling, spraying or the like. Or the cotton goods is washed, then treated with the fixing agent, again washed and dried. It-may also be only washed and dried.

During the'foregoing operations, the fabpart of the time. If the duration of the action of the alkali solution and of the halo hydrin is not too long, the material may be in the stretched condition throughout all the operations. It may, however, be stretched only during the action of the soda solution or after it has been impregnated therewith, and may remain stretched during the whole or a portion-of the treatment with the halo-hydrin,-

' and if necessary during the treatment with the acid or salt. The textile material may also be stretched during the washing operation, though this is advantageous only in respect of the silk-like lustre.

According to the process described in this example, there is obtained a high-grade, silklfikrla lustre, and a pleasing finish of elastic (b) The procedureis as in (a), with the exception that epichlorhydrin is used in place of a-mo'nochlorhydrin" or a-dichlor hydrin or ethylene-chlorhydrin.

'(c) The procedure is as in (a) or (b) with the exception that the action of the halo-hydrin is carried out at raised temperature. For this purpose, the material which has been impregnated with caustic soda solution and brought into contact with the halo-hydrin is maintained for 10 minutes to '1 hour "at a temperature of 100 C., for instance at 80 C.

(d) The procedure is as in (a), (b), or (0), with the exception that the caustic soda solution used isfof -1823Yper cent strengh,

' for example of 22.5 per cent strength instead of 25-40 per cent strength. The treated product has a very beautiful silky lustre.

(e) The procedure is as in (a), b), (c), or (d), with the exception that the alo-hydrin, or solutionor suspension thereof, preferably in the presence of British gum, is printed in the form of any desired pattern on the fabric which has been impregnated with the caustic soda solution and, if desired, dried before being printed.

Bleached or unbleached cotton fabric or yarn is impregnated with a solution of 10 ished as described in Example 1 (a). The

fabric may be stretched during or after the treatment with the soda solution. A silky lustreis produced. v

The procedure is as in any of Examples 1 I i (a) to 1 (d),-with the exception that instead of aqueous caustic soda solution of 18-40 per. cent strength there is used an alcoholic caustic soda solution of 18 per cent strength,

prepared, for example, by mixing 000 parts of caustic soda solution of 30 per cent strength with 400 cent strength.

The silk-like effect is excellent.

The procedure is exactly as in any of the preceding examples, with the exception that parts of alcohol of 96 perthe material is treated with a strong solution of sulphuric acid before being treated according to the invention. When sulphuric acid of 4950 Baum'gravity is used, the treatment with theacid may occur at room temperature for a period of from several seconds to several minutes, or even longer. When a stronger 361d 1s used, for example,

of 52-54 Baum gravity, the treatment'may v occupy only several seconds at room temperature, but a longer period if the acid be cooled to 0 C. or below.

The treatment with sulphuric acid mayi The procedure is just as in. the preceding examples, with the exception that the fabric is previously mercerized by anyknown mercerizing process.

The finished products maybe calendered,

schreinered, or beetled, or the like, in known manner. I Examples for obtaining pattern effects by means ofa reserve follow from those already given.

On treatment with a, halo-hydrin of a per cent strength at a poly-alcohol in the'presence-of an alkali the vegetable fibres are converted into hydroxyalkyl derivatives ofcellulose (in the case of a-mono-chlorhydrin a-1-2-dihydroxy-propyl cellulose, in the case of ethylene chlorhydrm a hydroxy-ethyl cellulose). Whether that conversion of the fibres takes place only on the surface of the fibres or in their deeper parts also, depends partly upon the concent-ration and amount of the alkali solution, partly on the quantity of the halo-hydrin used and partly on the temperature.

Consequently, on treating the finished fabric'with a mineral acid, for example, a hydro-halogen acid, (if concentrated in the cold, if diluted in the heat) a decomposition takes place, i. e. the poly-alcohol in question is liberated.

The expression textile material in the description and claims means, where the context permits, all vegetable fibres such as flex, linen, hemp, ramie, jute, and particularly cottoriand the like,- in the form of fabric of the pure vegetable product (such as pure cotton fabric) or mixed fibre, or yarn in skeins, cops or warps.

The expression agent which will precipitate 'oxyalkyl cellulose derivatives which are soluble in alkalihmeans acids, salts, acid salts, mixtures of acidsand salts, in short all precipitating agent's known in the viscose industry as well as organic acids or aqueous solutions thereof, alcohols, tannic acids, and formaldehyde.

"I claim:

1. A process for improving vegetable textile material which comprises acting upon it with ahalo-hydrin of.-a poly-alcohol in the presence of alkali metalhydroxide'.

2. A process'for improving vegetable textile material which comprises treating it with an alkali metal hydroxide solution and a halo-hydrin of a poly-alcohol. L

3. A process for improving vegetable textile material which comprises treating it s with a halo-hydrin and a solution containing alkali metal hydroxide in two steps,

4. A process for improving vegetable textile material, which comprises treating it with a solution. containing alkali metal hydroxide,

and thereafter acting on'itwith a halo-hydrin of a poly-alcohol.

5. A process for improving vegetable textile material, which comprises treating it with an alkali metal hydroxide solution, and thereafter acting on it with a'halo-hydrin of a polyalcohol in presence of the alkali solution remaining in the material.

6. A process for improving vegetable tex- "tile material, which comprises treating it with an alkali metal hydroxide solution, thereafter removing at least a portion of the water by drying, and acting on it with a halo-hydrin of a poly-alcohol.

7. A process for improving vegetable textile material, which comprises treating it with an alkali metai'hydroxide solution, and thereafter acting on it with a halo-hydrin of a polyalcohol mixed with a thickening agent.

8. A process for improving vegetable textile material, which comprises treating it with an alkali metal hydroxide solution, and thereafter coating it on at least one side with a halo-hydrin of a poly-alcohol. q

9. A process for improving vegetable textile material, which comprises treating it with a solution of an alkali metal hydroxide and thereafter coating it on at least one side with a halo-hydrin of a poly-alcohol mixed with a thickening agent.

10. A process for improving vegetable textile material, which comprises treating it with an alkali metal hydroxide solution and thereafter acting on it at certain parts with a halohydrin of a poly-alcohol.

11. A process for improving vegetable textile material, which comprises treating it with a solution of an alkali metal hydroxide andthereafter printing it with a halo-hydrin of a poly-alcohol mixed with a thickening agent.

12. A process for improving vegetable textile material, which comprises treating it at certain parts with an alkali metal hydroxide solution, and thereafter acting on it with a halo-hydrin of a poly-alcohol.

13. A process for improving vegetable textile material, which comprises treating it at a raised temperature in the presence of-an alkali metal hydroxide with a halo-hydrin of a poly.- alcohol.

14. A process for tile material, which comprises treating it with an alkali 'metal hydroxide solution, and thereafter acting on it at a raised temperature wit a halo-hydrin of a poly-alcohol.

a 15. A process for improving vegetable tex tile material, which comprises treating it in improving vegetable texwith a chlorhydrinof glycerine. c 16. A process for improving vegetable textile material, which comprises treating it with an alkali metal hydroxide solution, and thereafter acting-on it with a chlorhydrin of glycerine.

17. A process for improving vegetable textile material, which comprises treating it with an alkali metal hydroxide solution, and thereafter acting on it with a-monochlorhydrin.

18. A process for improving vegetable textile material, which comprises treating it with an alkali metal hydroxide solution, and thereafter acting on it with a chlorhydrin of glycerine in the presence of the alkali lye remaining in the material.

19. A process for improving vegetable textile material, whiohcomprises treating it with an alkali metal hydroxide solution, and thereafter acting on it at a raised temperature with a chlorhydrin of glycerine.

20. Aprocess' for improving vegetable textile material, which comprises acting on it in presence of an alkali metal hydroxide and of an alcohol with alcohoL- 21'. A process for improving vegetable textile material, which comprises actin on it in resence of'an alkali metal hydroxi c with a iialo-hydrin of a poly-alcohol, thereafter treating it with a material adapted to precipitate hydroxy alkyl derivatives of cellulose which are soluble in alkali, and then washing.

22. A process for improving vegetable textile material, which comprises treating it with an alkali metal hydroxide solution, thereafter acting on it with a halo-hydrin of a polyalcohol, and thereafter treating it with a material adapted to precipitate hydroxy alkyl derivatives of cellulose, which are soluble in alkali, and then washing. I

23. A process for improving vegetable textile material, which comprises treating it with an alkali metal hydroxide solution thereafter acting on it with a chlorhydrin of glycerine, thereafter treatin it with a material adapted to precipitate hy roxy alkyl derivatives of cellulose, which are soluble in alkali, and thereafter washing.

24. A process for improving vegetable textile material, which comprises acting on it in presence of an alkali metal hydroxide with a halo-hydrin of a poly-alcohol, and stretching the material during at least a portion of the process. I

25. A process for improving vegetable textile material, which comprises treating it with an alkali metal hydroxide solution, and thereafter'acting on it with a halo-hydrin of a halo-hydrin of a poly a poly-alcohol, and stretching the material during at least a portion of the process.

26. A process for improving vegetable textile material, which comprises treating it w1th an alkali metal hydroxide solution, and thereafter acting on it with a halo-hydrin of a poly-alcohol, and stretching the material durmg the treatment with the alkali solution.

27. A process for improving vegetable textlle material, which comprises treating it with an alkali metal hydroxide solution, and thereafter actin on it with a halo-hydrin of a poly-alcoho and stretching the material durm a portion of the treatment with the alkali so ution. I

28. A process for improving vegetable textile material, which com rises treating it with an alkalimetal hydroxi e.solution, and thereafter actmg on it with a chlorhydrin of glycerine, and stretching the material during at least a portion of the process;

29. A process for improving vegetable textile material, which comprises treating it with an alkali metal hydroxide solution, and thereafter acting on it with a chlorhydrin of glycerine, and stretching the material during the treatment the alkali solution.

30. A processf'or improving vegetable texwith an alkali metal hydroxide solutiom-and thereafter acting on it with a chlorhydrin of glycerine,'an d stretching the material during a portion of the treatment with the alkali solution.

31. A process for improving vegetable textile material, which comprises treating it with an alkali metal hydroxide solution, thereafter acting on it with a halo-hydrin of a polyalcohol, thereafter treatin" it with a material adapted to precipitate hydroxy alkyl derivatives of cellulose, which are soluble in alkali, and thereafter washing, and stretching the material during-at least a portion of the process.

32. A process for improving vegetable textile material, which comprises-treating it with an alkali metal hydroxide solution, thereafter acting on it with a chlorhydrin of glycerine,

then treating it with a material adapted to terials which have a silk-like lustre and which contain a 1-2dihydroxy-propyl-cellulose.

' 35. As new products, vegetable textile ma terials which have a silk-like lustre and which on decomposition with a hydrogen halide yield a poly-alcohol.

36. As new products, vegetable textile materials which have a silk-like lustre and which on decomposition with a hydrogen halide yield lycerine.

37 ellulosic textile material havin genits erated in its fibres an hydroxy 'alkyl er1vav tive of cellulose. 4

88. The process of improving cellulosic textile material which comprises converting it in part into a derivative of cellulose by the action of a halohydrin in the presence of causticalkali.-

39. The process of imparting a silky eflect to vegetable textile material which comprises generatin in'said material from a part thereof a. cellu ose derivative by the action of a halohydrin in the persefice of an alkali metal hydroxide. 1 c

40. Cellulosi'c textile material having generated in its fibres a derivative of cellulose which on treatment with a strong hydrogen halide decomposes into afolv alcohol; 4

In testimon whereof aiiix my signature.

. 1hr. LEON LILIENFELD.

'tile material, which-"comprises treating it. 

